Note: Descriptions are shown in the official language in which they were submitted.
CHS 04 1 016 - Foreign Countries NBT/AB/NT/V18.02.05
-1-
Pure-coloured, readily dispersible iron oxide red pigments with high grinding
stability
The present invention relates to pure-coloured, readily dispersible iron oxide
red
pigments with high grinding stability, to a process for preparing them, and to
their
use.
Iron oxide red pigments are used universally as colouring components in the
paint,
varnish, coating, building material, plastics and paper industries.
Iron oxide red pigments have advantages over organic red pigments. They can be
produced by cost-effective preparation processes, are environmentally
unobjectionable, are stable to light, are more readily dispersible, and
protect coloured
articles against damaging UV radiation.
Exacting requirements are imposed on the iron oxide red pigments in terms of
colour
purity, consistency of quality, and ease of processing (dispersibility,
grinding
stability).
In all applications for colouring varnishes, emulsion paints, coatings,
plastics,
building materials, paper, in foods and in products of the pharmaceutical
industry,
there is demand for iron oxide red pigments whose red component a' (measured
in a
mixture with white pigments - called reduction - according to CIELAB) is
particularly pronounced. The higher the red component a' determined for the
coloration, the purer in colour the red shade of the coloured medium appears
(for
example varnish, plastic, coatings, building material, paper).
Thus in the coatings industry a requirement which is imposed is that the
incorporation of the iron oxide red pigments into a coating system should
always
lead to coloration in a consistent shade, which as far as possible should be
independent of the duration of incorporation. The iron oxide red pigment is
incorporated into a coating system in industrial installations, such as bead
mills, in
which the pigment is exposed to mechanical forces, this grinding possibly
taking
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-2-
hours. A high measure of consistency of colour and/or quality is provided if
the
colour imparted by the iron oxide red pigment alters as little as possible in
the event
of fluctuations in the incorporation time. Iron oxide red pigments exhibiting
little
change in shade when the incorporation time is prolonged in a coating system
have a
high grinding stability. One measure of the consistency of colour is the hue
distance
0 h ab* which arises when the hue of two paint dispersions obtained from the
same
paint and pigment base materials in the same industrial installation, but with
different
incorporation times, is compared. The requirement here is for the resultant
hue
difference 0 h ab' to be as low as possible.
Moreover, in paint or plastics applications, for example, there is a
requirement that
the iron oxide red pigments should be uniformly distributed as easily as
possible in
the medium, in the form of primary particles; in other words, that they should
be
readily dispersible. What are not wanted are coarse pigment particles, which
in
applied paint films or coloured plastics lead, owing to their particle size,
to rough
surfaces ("pickling") or defects.
Red iron oxide pigments are prepared employing, generally, four methods
(T.C. Patton, Pigment Handbook, Vol. 1, 1973, p. 333):
1. Copperas red method
Elimination of water and sulphur oxides from iron sulphate (copperas) in a
multi-
stage operation gives pure-coloured and readily dispersible iron oxide red
pigments
with inadequate grinding stability.
2. Ferrite red method
Dehydration of yellow iron oxide (goethite), a-FeOOH, gives iron oxide red
pigments having good dispersibility but inadequate colour purity and
inadequate
grinding stability.
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-.3 -
3. Precipitated red method
Direct precipitation of iron oxide red from aqueous solution gives iron oxide
pigments having good dispersibility but inadequate colour purity and
inadequate
grinding stability.
4. Synthetic red method
Oxidation of synthetic black iron oxide (magnetite) gives iron oxide red
pigments
having good dispersibility and good grinding stability, but inadequate colour
purity.
By means of a range of technical measures, attempts have been made in the
past,
starting from the known preparation methods, to produce improved iron oxide
colour
pigments.
For instance, DE 35 121 24 Al and JP 47923/76 (Tone Sangyo) describe processes
for coating iron oxide red pigments with a colourless coating of 0.5 to 10
mol% of
Mg, Zn, Al, La, Y, Zr, Sn and Ca (DE 35 121 24 Al) or 0.3% to 10% of Al (JP
47923/76). The coating leads to iron oxide red pigments having improved colour
properties as compared with those of the uncoated iron oxide red pigments, and
having good dispersibility and an isoelectric point > 7. Iron oxide red
pigments
prepared in this way are distinguished by reduced flocculation as compared
with the
uncoated iron oxide red pigment starting materials used, but do not achieve
the
desired high colour purity.
Moreover, EP 0 290 908 Al describes a process for preparing pure-coloured iron
oxide red pigments having clustered pigment particles. These pure-coloured
iron
oxide red pigments are obtained by dehydrating yellow iron oxide (goethite =
a-FeOOH) which has been obtained, by a specific precipitating operation, in
the
form not of acicular, but instead of spherolitic iron oxide yellow. The Al-
containing
iron oxide red pigments thus obtained, although purer in colour than
conventional
iron oxide yellow pigments calcined to red, and also stable to grinding, are
nevertheless difficult to disperse.
CA 02507331 2005-05-13
CA 02507331 2012-03-09
30916-20
-4-
Furthermore, DE 35 00 470 Al describes a process for preparing pure-coloured
iron
oxide red pigments by oxidizing black iron oxide, this process leading to
pigments
purer in colour than conventional iron oxide red pigments prepared on the
basis of
conventional magnetite. The process starts out from specific, finely divided
magnetites, produced in the presence of high amounts of Fe(III) in aqueous
media,
these magnetites possibly having been produced in the presence of aluminium
salts
or phosphate salts. The iron oxide red pigments obtained after oxidation,
possibly
including aluminium or phosphorus as dopants, are stable to grinding and
readily
dispersible, but do not achieve the desired colour purity.
It is therefore clear that neither by means of the four abovementioned methods
(T.C. Patton, Pigment Handbook, Vol. 1, New York 1973, p. 333) of preparing
red
iron oxide pigments nor by modifications to the methods, such as coating of
iron
oxide red pigments with colourless aluminium compounds, nor by doping with
aluminium and phosphorus, are improved iron oxide red pigments obtained which
differ in their advantageous combination of properties, comprising high colour
purity
at the same time as high grinding stability and good dispersibility, from
conventionally known iron oxide red pigments.
The invention provides improved iron oxide red pigments which exhibit not only
high colour purity but also high grinding stability and good dispersibility.
This has been achieved in the form of iron oxide red pigments having an a*
value, measured in white reduction (mixed with white paste) according to
CIELAB
units in accordance with DIN 6174, after 15 minutes of dispersing in an
Olbrich
shaker, of from 26.5 to 30, in particular from 26.5 to 28.5, which on paint
dispersion
in an Olbrich shaker, with an increase in the dispersing time from 15 to 120
minutes,
exhibit a hue difference A h ab* in accordance with DIN 6174 of < 1.1, in
particular
< 0.8.
CHS 04 1 016 - Foreign Countries
-5-
The iron oxide red pigments, on paint dispersion in an Olbrich shaker with an
increase in the dispersing time from 15 to 120 minutes, preferably exhibit a
shade
difference A a in accordance with DIN 6174 of < 0.8, in particular < 0.6.
The iron oxide red pigments, on paint dispersion in an Olbrich shaker with an
increase in the dispersing time from 15 to 120 minutes, preferably exhibit a
shade
difference A bin accordance with DIN 6174 of < 1.8, in particular < 1.3.
The iron oxide red pigments further exhibit, as compared with Bayferrox 110
M,
with a dispersion time of 15 minutes in an Olbrich shaker, an a* value which
is
advantageously higher by 0.5 to 4 units, as measured in white reduction
according to
CIELAB units in accordance with DIN 6174. Preferably the iron oxide red
pigments,
as compared with Bayferrox 110 M, with a dispersion time of 15 minutes in an
Olbrich shaker, have an a value which is higher by 0.7 to 2 units, measured in
white
reduction according to CIELAB units in accordance with DIN 6174. Furthermore,
on
paint dispersion in an Olbrich shaker with an increase in the dispersing time
from 15
to 120 minutes, the iron oxide red pigments have a hue difference A h ab* in
accordance with DIN 6174 of < 1.1, in particular < 0. 8, or a shade difference
A a in
accordance with DIN 6174 of < 0.8, in particular < 0.6, or a shade difference
A b- in
accordance with DIN 6174 of < 1.8, in particular < 1.3. Bayferrox 110 M (CAS
No.
1309-37-1 from Bayer Chemicals AG) in the sense of the invention denotes a
powdery, red Fe2O3 pigment having a density of about 5 g/cm3 (measured at 20 C
in
accordance with DIN ISO 787/10) and a pH of 4-8 at 50 g/l water in aqueous
suspension in accordance with DIN ISO 787/9; it is used as a colorant.
The iron oxide red pigments preferably have a dispersibility according to DIN
ISO
1524 (2002) in the extended form, as the "3-box" method, of better than 15-25-
40.
The iron oxide red pigments comprise preferably clustered pigment particles
whose
clusters comprise at least five bead-like parts merged with one another.
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-6-
The iron oxide red pigments contain preferably 0.5 to 10 mol% of a compound
from
the group Mg, Zn, Al, La, Y, Zr, Sn and/or Ca, based on the iron oxide red
pigments.
Mg, Zn, Al, La, Y, Zr, Sn and/or Ca are preferably present on the surface and
in the
iron oxide red pigment.
The invention also provides a process for preparing iron oxide red pigments,
characterized in that
= an iron oxide yellow pigment built up on the basis of an iron oxide yellow
seed
= is coated in the presence of Mg, Zn, Al, La, Y, Zr, Sn and/or Ca, in
particular
by spraying on, grinding on and/or precipitating on, so that the amount of
elements from the group Mg, Zn, Al, La, Y, Zr, Sn and/or Ca is 0.5 to
10 mol%, based on the total iron content of the iron oxide yellow pigment;
= the iron oxide yellow pigment is calcined to give red clinker;
= and the red clinker is ground to iron oxide red pigment.
The iron oxide yellow pastes used as precursors may be prepared preferably in
accordance with DE 3 326 632 Al, and comprise highly branched pigment
particles.
A preferred process for preparing the iron oxide pigments of the invention is
characterized in that the preparation of the iron oxide yellow seed of the
iron oxide
yellow pigment (a-FeOOH) intended for coating takes place in the presence of
compounds of the elements B, Al, Ga, Si, Ge and/or Sn in amounts of 0.05% to
10%
by weight, calculated as oxides in accordance with the maximum valency of the
elements, based on the arithmetically precipitated a-FeOOH seed, the pigment
formation step takes place in a manner customary for the skilled person, the
salt
liquor is separated from the resultant yellow slurry, and the isolated iron
oxide
yellow paste is coated prior to calcining to give the iron oxide red pigment.
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-7-
In this process, first of all, preferably in accordance with DE 3 326 632 Al,
a seed is
produced with degrees of precipitation of from 20% to 70% in the presence of
compounds of the elements B, Al, Ga, Si, Ge and/or Sn at temperatures from
room
temperatures up to 70 C. A pigment is grown on this seed. Pigment formation to
form iron oxide yellow may take place by the method of Penniman in the
presence of
metallic iron, by the aniline method or by the precipitation method. In the
case of the
precipitation method it is possible to use iron salts purified by
preprecipitation.
In the case of the precipitation method the pigment is formed preferably at
constant
pH in the range 2.8 to 4.5 or with stepwise increase in pH, in the course of
pigment
formation, from levels < 3 in units of 0.1 to 0.2/step to levels of 3.8 to
4.5.
After the end of pigment formation, the products, in the form of a precursor
to the
preparation of the innovative iron oxide red pigments, comprise salt-
containing
yellow slurries, which can be washed preferably to low salt content and, if
desired,
can be dried.
The coating of the yellow pigments obtained as an intermediate in accordance
with
the invention with a colourless coating of 0.5 to 10 mol% of Mg, Zn, Al, La,
Y, Zr,
Sn and Ca takes place in such a way that a coating of a compound of one or
more
elements from the group Mg, Zn, Al, La, Y, Zr, Sn and Ca is formed on the iron
oxide yellow pigments by spraying on, grinding on and/or precipitating on,
such that
the amount of elements from the group Mg, Zn, Al, La, Y, Zr, Sn and Ca is 0.5
to
10 mol%, based on the total iron content of the yellow pigments.
When the coated intermediate is calcined, the particle size of the
intermediate, the
nature and amount of the coating, the temperature profile and the residence
time all
affect, in a known way, the colouristic properties of the resultant iron oxide
red
pigment.
The oven product, the red clinker, is ground in a way which is usual in the
art, the
skilled person being able to select from a multiplicity of grinding apparatus.
By way
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-8-
of example, but without limitation, mention may be made of air jet mills,
steam jet
mills, Raymond mills and bead mills.
Surprisingly, the iron oxide red pigments obtained after grinding differ from
conventional, known iron oxide red pigments in high colour purity in
combination
with high grinding stability and good dispersibility.
The invention also provides for the use of the iron oxide red pigments for
colouring
products of the paint, varnish, coatings, building material, plastics and
paper
industries. The iron oxide red pigments of the invention can be used, further,
in foods
and in products of the pharmaceutical industry, such as in tablets, for
example.
The invention is illustrated in more detail with reference to the following
examples,
without any intention that these examples should impose any restriction on the
invention.
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-9-
Examples
Description of the measurement methods used
The tests were carried out by way of example in a medium-oil alkyd resin
(Alkydal
F 48, Bayer Polymers, Leverkusen). For dispersion, the pigment preparation was
premixed in a dissolver, in a manner known to the skilled person, and then
shaken in
an rm5000 paint mixer from Olbrich, D-58675 Hemer, with glass beads (0 1 mm)
for the times indicated. The pigment pastes were let down and applied with a
manual
coating bar in a film thickness of 120 m to a coated white card. To
investigate the
reduction, the mixture of red paint and white paint was applied in the same
way to a
coated white card. After drying at room temperature for at least 16 hours, the
samples were evaluated colorimetrically. Colorimetry took place using a
Dataflash
2000 from Datacolor. The colour differences were determined according to DIN
6174 (CIELAB values).
Preparation of the red pigment paste
Weigh out 87.5 g of medium-oil, air-drying alkyd resin based on drying
vegetable
fatty acids in white spiritlxylene, Bayer Polymers AG, 6.0 g of aromatic
hydrocarbon
mixture, consisting primarily of trimethyl-, propyl- and methylethylbenzyenes
(with
the formula C6H3(CH3)3) and 175 g of red pigment into a 250 ml tinplate can
(7.5 cm) and predisperse with a dissolver at 5000 rpm for 10 minutes (disc 4
cm;
peripheral speed about 10.5 m/s).
Weigh out 140 g of the above mixture and 230 g of glass beads into a 250 ml
wide-
neck glass bottle with screw closure, and shake with an rm5000 colour mixer,
Olbrich ("Olbrich shaker" below). After the end of the dispersing time, remove
glass
beads by sieving, and let down pigment paste.
Preparation of the letdown solution
CA 02507331 2005-05-13
CHS 041 016 - Foreign Countries
-10-
Weigh out 253.9 g of medium-oil, air-drying alkyd resin based on drying
vegetable
fatty acids in white spiritlxylene, Bayer Polymers AG, 20.6 g of solvent
naphtha 100,
5.7 g of methoxypropyl acetate, 2.4 g of anti-skinning agent containing 2-
butanone
oxime, 55% in white spirit, Borchers GmbH, 4.9 g of silicone-based levelling
assistant containing polydimethylsiloxane and octamethylcyclotetrasiloxane,
Borchers GmbH, 1% in xylene, and 11.3 g of mixed metal dryer (siccative)
containing cobalt octoate, calcium octoate, zinc octoate and zirconium octoate
as a
mixture in solution in white spirit with an aromatics content of not more than
1%,
Borchers GmbH, into a suitable vessel and homogenize thoroughly.
Letdown
Mix 7.5 g of pigment paste and 16.0 g of letdown solution thoroughly in a
suitable
vessel.
Preparation of the white paint for reduction
Weigh out 35.0 g of medium-oil, air-drying alkyd resin based on drying
vegetable
fatty acids in white spirit/xylene, Bayer Polymers AG, 30.0 g of solvent
naphtha 100,
100 g of titanium dioxide white pigment, Kerr McGee and 230 g of glass beads
into a
250 ml wide-neck glass bottle with screw closure and shake for 30 minutes with
an
rm5000 paint mixer from Olbrich. After the end of the dispersing time, remove
glass
beads by sieving, and let down pigment with a homogeneous mixture of 226.2 g
of
medium-oil, air-drying alkyd resin based on drying vegetable fatty acids in
white
spiritlxylene, Bayer Polymers AG, 16.0 g of solvent naphtha 100, 8.0 g of
methoxypropyl acetate, 2.15 g of anti-skinning agent containing 2-butanone
oxime,
55% in white spirit, Borchers GmbH, 4.3 g of silicone-based levelling
assistant,
Borchers GmbH, 1% in xylene, and 10.0 g of mixed metal dryer (siccative)
containing cobalt octoate, calcium octoate, zinc octoate and zirconium octoate
as a
mixture in solution in white spirit with an aromatics content of not more than
1%,
Borchers GmbH.
Preparation of the white tint (reduction)
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-11-
Mix 2.76 g of red paint with 10.76 g of white paint thoroughly in a suitable
vessel.
Determination of dispersibility
The paint dispersed in the Olbrich shaker by the method described above is
placed on
the top end of the grindometer block, which has been wiped clean shortly
beforehand, and is drawn down slowly with the scraper at right angles. The
particle
size must be read off immediately. The evaluation is made along the lines of
DIN
ISO 1524 (2002) in the extended form as the "3-box" method in accordance with
test
method No. 004 of 1995-05-15 (Bayer Chemicals, Business Unit Inorganic
Pigments), as follows:
Equipment Pendraulik stirrer, dissolver disc, 0 40 mm
Tinplate can, 250 ml
Grindometer block, 0-100 m
Balance
Kitchen timer
Spatula
Small bottle with snap-on lid
Auxiliaries Alkydal F 681, 75% in white spirit
Alkydal F 681, 45% in white spirit
Procedure
Millbase formulations of the Bayferrox pigments
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-12-
Red and black pigments Yellow
pigments
Alkydal F 681, 75% 100 g 110 g
Bayferrox 220 g 70 g
exception: 110 M 180 g
Binder is charged to the stirring vessel and the pigment is added in portions
at
1000 rpm and stirred in. The stirrer shaft, dissolver disc and edge of the can
are
cleaned to remove unwetted pigment particles, using the spatula or sheet of
card. The
dispersing apparatus in the stirrer is then fixed concentrically, maintaining
the
distance from the base, and the millbase is dispersed at 5000 rpm for 10
minutes.
In a small sealable bottle the millbase is mixed thoroughly with a 45%
strength
Alkydal F 681 binder solution in white spirit in a ratio of 1:1. The diluted
sample is
placed on the top end of the grindometer block, which has been wiped clean
shortly
beforehand, and is drawn down slowly at right angles using the scraper. The
uniform
drawing of the scraper spreads the sample in the groove, which has a division
of 0-
100 pm. The particle size must be read off immediately.
Evaluation
The method is described in DIN ISO 1524, "determination of fineness of grind
(particle size)", and as a characteristic value, accordingly, the value is
read off (in
m) "below which a relatively large number of pigment particles become visible
as
bits or scratches on the surface (of the spread-out paint). Individual bits or
scratches
that may have occurred are not taken into account in this consideration (Fig.
1)."
The "3-box" method employed for testing the pigments is an extended form of
reading off, in which three values are reported as the result.
The main region in the form of a close coherent array of bits, above it a
region with a
moderately high concentration of bits, and finally, over that, a region with a
very low
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-13-
concentration of bits (virtually individual bits, but which occur
reproducibly)
(Fig. 2).
Therefore, a trio of values is recorded, which characterizes the upper limits
of the
three regions indicated. A grindometer spread according to Fig. 2 is assessed,
accordingly, as follows: < 10/25/35 m.
By virtue of their position within the three-point system, the three values
clearly
indicate to what kind of the three arrays of bits they can be assigned. If, in
specific
cases, one of the three regions does not appear, then a line (for examples of
this see
Figs. 3, 4 and 5) appears at the point in question.
If the concentration of bits within a region is remarkably high (but without
reaching
the density of the adjacent region), this can be indicated by underlining the
limit
value in question. An example of this is shown in Fig. 6 (in comparison to
Fig. 2).
Example 1 (comparative)
The iron oxide yellow pastes or suspensions used as precursors were prepared
in
accordance with DE-A 3 326 632 Al, Example 2, and comprise highly branched
pigment particles.
The material, obtained in the form of suspension or paste, is filtered through
a filter
press and subsequently washed with fully deionized water until the filtrate
has a
conductivity of < 2 mS. 50 kg of the filtercake are stirred out with 501 of
water in a
1501 cask and subsequently dried. 5 kg of the dried material were subsequently
calcined at 740 C (measured in the product) in a suitable apparatus for 30
minutes
after reaching the product temperature.
The calcined material was introduced into a coating drum, and 1 g of 50%
strength
trimethylolpropane solution in water was sprayed on uniformly per 100 g of
pigment,
using a two-fluid nozzle. Subsequent steam jet milling was carried out in a
steam jet
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-14-
mill from Alpine (internal diameter: 25 cm) with a product feed of 10 kg/h for
18 kg/h propulsion steam and 45 kg/h grinding steam.
Example 2
The iron oxide yellow pastes used as precursors were prepared in accordance
with
DE-A 3 326 632 Al, Example 2, and comprise highly branched pigment particles.
The material, obtained as suspension or paste, is filtered via a filter press
and
subsequently washed with fully deionized water until the conductivity of the
filtrate
is < 2 mS. 50 kg of the filtercake are stirred out with 501 of water in a 150
1 cask and
subsequently, with stirring, 1.071 of aluminium sulphate solution
(concentration
100 g/l Al, calculated as A1203) are added over the course of 15 minutes.
Following
the addition the pH of the suspension was 3.2. Subsequently 0.723 1 of sodium
aluminate solution (concentration 300 g/l, calculated as A1203) was added over
the
course of 15 minutes. The pH of the suspension was subsequently 7.03. Finally
a pH
of 8.5 was set using sodium hydroxide solution (NaOH), followed by stirring
for 60
minutes more. Following the subsequent stirring period, the batch was filtered
via a
filter press and the solid product was washed with water to a conductivity of
< 500 S. The filtercake was subsequently dried at 120 C. 5 kg of the dried
material
was subsequently calcined at 750 C (measured in the product) in a suitable
apparatus
for 30 minutes after reaching the product temperature.
The calcined material was introduced into a coating drum, and 1 g of 50%
strength
trimethylolpropane solution in water was sprayed on uniformly per 100 g of
pigment,
using a two-fluid nozzle. Subsequent steam jet milling took place in a steam
jet mill
from Alpine (internal diameter: 25 cm) with a product feed of 10 kg/h for 18
kg/h
propulsion steam and 45 kg/h grinding steam.
The finished material obtained in this way was tested in accordance with the
methods
indicated above.
Example 3
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-15-
The iron oxide yellow pastes used as precursors were prepared in accordance
with
DE-A 3 326 632 Al, Example 2, and comprise highly branched pigment particles.
The material, obtained as suspension or paste, is filtered via a filter press
and
subsequently washed with fully deionized water until the conductivity of the
filtrate
has is < 2 mS. 50 kg of the filtercake are stirred out with 50 1 of water in a
150 1 cask
and subsequently, with stirring, 2.141 of aluminium sulphate solution
(concentration
100 g/l Al, calculated as A1203) are added over the course of 15 minutes.
Following
the addition the pH of the suspension was 3.08. Subsequently 1.45 1 of sodium
aluminate solution (concentration 300 g/l, calculated as A1203) were added
over the
course of 15 minutes. The pH of the suspension was subsequently 8.4. Finally a
pH
of 8.5 was set using sodium hydroxide solution (NaOH), followed by stirring
for 60
minutes more. Following the subsequent stirring period, the batch was filtered
on a
filter press and the solid product was washed with water to a conductivity of
< 500 S. The filtercake was subsequently dried at 120 C. 5 kg of the dried
material
was subsequently calcined at 790 C (measured in the product) in a suitable
apparatus
for 30 minutes after reaching the product temperature.
The calcined material was introduced into a coating drum, and 1 g of 50%
strength
trimethylolpropane solution in water was sprayed on uniformly per 100 g of
pigment,
using a two-fluid nozzle. Subsequent steam jet milling took place in a steam
jet mill
from Alpine (internal diameter: 25 cm) with a product feed of 10 kg/h for 18
kg/h
propulsion steam and 45 kg/h grinding steam.
The finished material obtained in this way was tested in accordance with the
methods
indicated above.
Example 4
The iron oxide yellow pastes used as precursors were prepared in accordance
with
DE-A 3 326 632 Al, Example 2, and comprise acicular, highly branched pigment
particles.
CA 02507331 2005-05-13
CHS 041 016 - Foreign Countries
-16-
The material, obtained as suspension or paste, is filtered via a filter press
and
subsequently washed with fully deionized water until the conductivity of the
filtrate
is < 2 mS. 50 kg of the filtercake are stirred out with 50 1 of water in a 150
1 cask and
subsequently, with stirring, 3.21 1 of aluminium sulphate solution
(concentration
100 g/l Al, calculated as A1203) are added over the course of 15 minutes.
Following
the addition the pH of the suspension was 3.14. Subsequently 1.34 1 of sodium
aluminate solution (concentration 300 g/l, calculated as A1203) were added
over the
course of 15 minutes. The pH of the suspension was subsequently 5.4. Finally a
pH
of 8.5 was set using sodium hydroxide solution (NaOH), followed by stirring
for 60
minutes more. Following the subsequent stirring period, the batch was filtered
via a
filter press and the solid product was washed with water to a conductivity of
< 500 S. The filtercake was subsequently dried at 120 C. 5 kg of the dried
material
was subsequently calcined at 800 C (measured in the product) in a suitable
apparatus
for 30 minutes after reaching the product temperature.
The calcined material was introduced into a coating drum, and 1 g of 50%
strength
trimethylolpropane solution in water was sprayed on uniformly per 100 g of
pigment,
using a two-fluid nozzle. Subsequent steam jet milling took place in a steam
jet mill
from Alpine (internal diameter: 25 cm) with a product feed of 10 kg/h for 18
kg/h
propulsion steam and 45 kg/h grinding steam.
The finished material obtained in this way was tested in accordance with the
methods
indicated above.
Comparative examples
Comparison pigment is the commercially available Copperas Red R1599D from
Elementis.
Table 1: Test results
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-17-
Testing in F48 (reduction) in accordance with DIN 6174; Report in CIELAB
units
Sample Dispersion a* b* Shade Shade Hue difference
Olbrich difference A a* difference A b* A h* in
shaker (in in comparison in comparison comparison to
minutes) to 10-minute to 10-minute 10-minute
dissolver dissolver dissolver
dispersion dispersion dispersion
R1599D 15' 27.04 18.35 0.23 0.39 0.20
R1599D 120' 28.01 21.14 1.15 2.58 1.47
Example 1 15' 26.57 16.71 0.42 0.56 0.26
Comparative
Example 1 120' 27.42 19.00 1.25 2.45 1.40
Comparative
Example 2 15' 26.73 28.21 0.29 0.46 0.23
Example 2 120' 27.17 19.42 0.87 1.69 0.93
Example 3 15` 26.56 18.50 0.27 0.52 0.28
Example 3 120' 27.13 20.02 0.70 1.48 0.83
Example 4 15' 26.56 18.49 0.26 0.40 0.19
Example 4 120' 27.19 20.37 0.75 1.67 0.95
All of the examples and comparative examples given in Table 1, and also the
comparison pigment R1599D, have a more pronounced red value a than Bayferrox
110 M from Bayer Chemicals AG, which was measured at a = 25.66 in F48
reduction at 15 minutes in an Olbrich shaker in accordance with DIN 6174.
Bayferrox 110 M from Bayer Chemicals AG serves as a reference for the colour
locus at for the specified examples and comparative examples. By simple
formation
of differences between the at values determined for 15 minutes in the Olbrich
shaker
and the at value of 25.66 for Bayferrox 110 M, it is possible to calculate
the
difference in shade between the comparison pigment of the comparative examples
and the inventive examples.
CA 02507331 2005-05-13
CHS 04 1 016 - Foreign Countries
-18-
Table 2: Comparison of dispersibility
Sample Dispersing time Dispersing value in m
Example 1 30'Olbrich shaker 15-30-40
comparative
Example 2 30'Olbrich shaker 10-25-30
Example 3 30'Olbrich shaker <10-15-30
Example 4 30'Olbrich shaker <10-15-25
R1599D 30'Olbrich shaker <10-10-20
Fig. 7 shows the effect of dispersing time on as. The y axis shows the change
of at,
while the x axis shows the time spacings of 5 min, 15 min, 30 min, 60 min and
120 min, in each case for the pigments R1599D, Example 1 (comparative),
Example 2, Example 3 and Example 4.
Fig. 8- shows the effect of dispersing time on b*. The y axis shows the change
of b*,
while the x axis shows the time spacings of 5 min, 15 min, 30 min, 60 min and
120 min, in each case for the pigments R1599D, Example 1 (comparative),
Example 2, Example 3 and Example 4.
Fig. 9 shows the effect of dispersing time on h*. The y axis shows the change
of h
while the x axis shows the time spacings of 5 min, 15 min, 30 min, 60 min and
120 min, in each case for the pigments R1599D, Example 1 (comparative),
Example 2, Example 3 and Example 4.
Figs. 7-9 demonstrate that the iron oxide red pigments of the invention
exhibit a
higher grinding stability than the prior art.
CA 02507331 2005-05-13
